Composition for effecting agglomeration of solids in aqueous suspensions



' nation is then Patented July 2, 1946 lcoMrosrr'IoN.-,ron Erracrm f vsoLms mlioUEoUs sUs-H .v-

l EBATION OF PENSIONS Richard ruu',.rr.,"1hn ee, Gowan a, Cooper Corporations, Go

R. McK

G 4.costola- 1 f N- nahm-a, 'machu-les Y.. assignors No Application November 21,1944, 4

I serial No. 564,559 v "I'his'lnvention relates to lcompositions for effectin'g the agglomeration of solids inA aqueous suspensions, preliminary tothe removal or recovery of the solids.

-By agglomeration we'mean the balling or hold- L ing together, the ilocculation, the precipitating, the ilotation or setting of the originally suspended solids, thereby permitting separation of the solids from the aqueous medium 'by means or methods well known in the trade.

Previous methods for agglomeration of solids suspended in aqueous mediums are largely concerned with the chemical formation of an auxiliary iloc within the system, resulting primarily in a physical entanglement of the suspended solids within the iloc. 'I'his general procedure is commonly followed in the treatment of raw water and/or industrial wastes where by the addition of alums, copperas or other iron compounds to the aqueous suspensions of solids, a gelatinous tloc of valuminum or iron hydroxides is formed under controlled pH conditions, resulting in the occlusion or entanglement of the suspended solids with the oc. The resultant noo-solids combisettled out, filtered, or floated as is desired, depending on the equipment used.

' Another method, not as well known as the chemical lloc, comprises the addition of a colloid such as animal glue to the suspension of solids, resulting in an agglomeration of the solids through neutralizing the electrical charges of like nature carried by the individual particles in aqueous suspension. In this method, it is generally understood that in a aqueous suspension of solids, each particle carries an electrical charge and that the charges are all of like polarity, either positive or negative, and that the stability of the suspension is dependent upon the mutual repulsion of the individual particles bearing like charges. If the charges are neutralized, agglomeration, precipitation, occulation, flotation, or settling of the solids will result. 'I'his procedure has been successfully used in agglomerating raw or process waters carrying clay, silica and silt materials, by adding a one per cent solution of animal glue to the systemA at the rate of about one gallon per 1000 gallons oi' suspension. An agglomeratlon of solids takes place which results in settling ofthesolids. 'I'he success of this process is dependent on the amphojwell, that lthe 7 Claims. (Cl. 2.52,.-181) vof 4.2 to 5.5 or is brought to this range by the use of caustic alkalis, acids alums,'etc. as the case mayrequiref, Animal glue in this pH range is nearly iso-electric, bearing 'no charge or `a balance of positive and negative 'charges,'and in such a state is capable of adsor'bing either positive or negative charges carried by the individual particles of the suspension. mal glue, as in the above example, the glue colloid apparently adsorbs the presenten the individual particles resulting in a neutralizing of the particle charges, thus 'destroying the stability of the suspension and permitting the particles to agglomera It is known,l as presence of trivalent aluminum,

' iron and/or chromium ions in theoriginal aqueous suspension of solids is required for -e'ectiveA peratures preferablybelow', 65i "ripening to insure adequate given system oi.' an

teric nature oi' animal glue, i. e., its ability to absorb or adsorb relatively large electrical charges, either positive or negative, depending on the pH control. 'I'he pH of the system in the case of this suspension is generally in the. range action. If, from'gthe nature vof insufficient of such ions the suspension, areA present, it iscusso-calledjmordanting etlect. Under the usualcontrolsj.l such additions are not by themselves,suillcient to promote theformation of a chemical iloc. I, This use of animal glue as an auxiliary agglomeratingfagent has not met with widespread use, due to a number of factors; the action is at times sluggish; for best results'the gluesolution must becorrected toa pHof 4.7 (iso-electric point), a critical control; the prepared auxiliary glue solution must be aged for-24 hours at .tem-

F.l 'for proper reactivity; the aqueous suspensionfof solidsvmustvvbe vproperly balanced as to pH and mordant; thefversatility of the auxiliary glue solution was not great under iluctuating conditions of theaqueous suspension of solids. 'I'he ripening` of the auxiliaryfglue -solution by aging for 24 hours at a cool tempera` ture and in a quiet state is 'believed to result in the development of larger, more hydrated. co1- loidal glue particle structure, which in someman-A ner promotes more eil'ective reactive results'.`- f,

One of thel objects of, this inventionis toprovide an improved agglomerating*solution-,which an improvedsolution of this type which actsmuch morey rapidly and positively on va `suspensionthan It is alsoany object to provide,v an improved which canibe reliedfupon to produce ythe-.desired eil'ect on 'a suspension of the suspension.

electrical charges vunder varying conditions carbonate, trisodium phosphate Other objects and advantages of this invention will appear from the following description and claims;

'l We have found that the reactivity of an animal glueA auxiliary` agglomerating solution can be markedly increased in intensity and. eect if a moderately Astrong negative charge is induced upon the glue colloid before addition of the solution to an aqueous suspension of solids mordanted in the usual maner and that the induced negative chargeis still more effective if the glue colloid is maintained at its-maximum lpoint of hydration. These conditions are easily effected by the additionof sufficient alkaline' materials to approximately a 1% animal `glue solution to give a resultant pH in the range of 8.0 to 10.0. A pH of 8.5 is especially 'effective with many glues tested. For our purposes, we prefer the use'of caustic soda or potash as the alkalinev medium, due to low cost, availability, and ease of handling. Ammonia, borax, silicate of soda,

and'other alkalies may be used for` this purpose although the: carbonates and phosphates are not as effective as the others due possibly to a depressing action on the glue. hydration and/or other side reactions. The amount of alkaline material required to fulfill the above conditions will vary,

hydrat1on of the animal glue colloid is found in the pH range of 8.0 to 10.0, depending on the previous case history of the particular glue (manufacturing process and raw stock). The preferred pH control for optimum results for a given type or commercial sourcev of animal glue is easily found by simple practical laboratory trials and offers no .diiculty.

We have found that the further addition of a mildly alkaline colloid selected from a groupconsisting of rosin size, rosin soap, sodium resinates and other waterA soluble commercial soaps to the glue solution, serves to increase the effectiveness and versatility of the agglomerator under many conditions of practical use. The function of the mildly alkaline soap-like colloid is not completely understood, and although it appears to impart a slightly more pronounced agglomerating action, its main function appears to aid in the coalescing of the agglomerated particles, promoting easier subsequent settling, filtering, or flotation, approximately vfrom 3% to 12% (dry basis) of this alkaline colloid, based on the dry weight of the glue may be used. The term mildly alkaline water-soluble soap-like colloid is herein used to include rosin size, rosin soap, sodium resinates and water-soluble commercial soaps.

rThe auxiliary glue composition so prepared gives a glue solution wherein the highly hydrated glue colloid carries a negative charge of considerable magnitude. The addition of small quantities of this composition to a mordanted aqueous suspension of solids in a pH range of approximately 4.0 to 6.0, results in an immediate agglomeration of the solids, promoting eflicient clarication of the suspension. It is believed that the magnitude of the negative electrical charge carried by the highly hydrated glue colloid rieulime water, sodium- This preferred auxiliary agglomerating glue solution is ready for immediate use after preparation, since it requires no aging or ripening period for development of reactivity as is required with lprevious auxiliary agglomerating glue solutions. This improved feature is of commercialimportance, as it permits rapid preparation and use of the solution as-needed, and eliminates the need for extra storage tanks prevously required for aging of the solution.

This preferred auxiliary agglomerating glue solution provides a sharper, more effective agglomeration of the suspended solids than the previously known compositions, thus providing for a clearer effluent and a higher efiiciency of solids recovery.

This preferred auxiliary agglomerating glue versatility in eiective solution possesses a greater use over a far wider range of'variable conditions and properties of heretofore possible *with previously known agglomerating solutions of animal glue. This characteristic is desirable as it is well known that systemsof "solid suspensions vary constantly in commecialperations as to total solids, percentage I of mordant; pH, etc.

depending onk the hardness and pH of the water used. The maximum I tralizes the positive charges carriedby the susadjusted to accomplish'this end:

y (1) Glue poun 100 `Caustic soda or caustic potash .do 0'.5to3.0 Wat-er -gal1ons.. 1,200 f (2) Glue pounds-- Borax in `@to 8 Water gallons 1,200

(3) Glue pounds-- 100 Calcium oxide (lime) do 1 4 to 8 Water -gallons 1,200

(4) Glue pounds-; 100 Trisodium phosphate do 7 to 12 Water gallons 1,200

(5) Glue pounds 100 Ammonia (as Nl) do 2 to 4 Water y vallone 1,200

(6) Glue pounds 100 Silicate of soda do.. 1 to 3 Water gallons 1,200

(7) Glue pounds 100 Soda ash do 1 to 3 Water gallons 1,200

0 (8) Glue pounds 100 Rosin size or mildly alkaline soap poundsn 10 Caustic soda dn 3 Water gallons 1,200

The following formulas illustrate by way of examples a few embodiments of this invention. The exactvquantities of alkalies` required are subject to considerable variation, ldue to variation in pH of the glue and the hardness of the particular water used. Qn completion, the pH of the auxiliary agglomerating solution-should fall in the pH range of 8.0 to 10.0, the amount of alkali being the suspension of1 solids than I- in the preparation.

eratii'ig solutions:

- as they pass upon the forming To each of formulas 1, 2, 3, 4, 5, 8, and 7, 3 to 12 pounds rosin size, sodium resinates, or commercial soap (all on a dry basis) may be added.

In preparing the above compositions, the animal glue preferably is ilrst soaked in an excess of cold water until soft (1 pound kdry glue per ofour improved agglomeratingsolution promotes gallon of water), then melted at 140 F., and l diluted out with approximately of the formula weight of water in a suitable storage tank. 'I'he diluted rosin size, sodium resinate, or soap is added (if to be used), followed by a dilute solution of the alkaline material, and nally, the balance of the water required to satisfy the formula is added. Three quarts oi' formalin per 1000 gallons of solution may be added as a preservative.

In the case of Formula 3. the lime, on being added to water. is completely soluble in the igooganons primer The following examples will serve to demonstrate the practical use oi the improved agglom- Ezample I use. For best paper formation and even retention` of the fillers, it is extremely desirable to hold as much of the filler and iber on the wire or cylinder screen as is possible on the first pass of the fiber-1111er suspension over the paper forming medium. This is especially true of the ne fibers which are most richly sized and whose retention in the sheet promotes increased strength and even formation. This is fillers, as it is desired to hold a uniform ratio of filler to iiber upon the sheet for uniform opacity and quality of the paper sheet.

'I'he addition of the preferred auxiliary agglomerating glue solution to the dilute fiber-filler suspension just before the suspension passes to the forming medium in the ratio of approximately 1 gallon per 1000 gallons of suspension promotes an immediate agglomeration of the fibers-fillers medium. 'I'his agglomerating action ties in the flne and coarse bers and illlers such that tention upon the forming medium is greatly increased, promoting a more even formation, a stronger sheet, a faster draining sheet, with minimum recirculation of white water solids.

Example II In the recovery of fibers and llers from those paper mill white waters which normally pass to settling tanks or to other commercial recovery systems or savealls. the use of the improved auxiliary agglomerating glue solution provides a highly mately 1 gallon per 1000 gallons of white water.)

An immediate agglomeration takes place promoting rapid settling of the `fiber-solids, which are removed in the usual manner` as, for example, the use of a continuous bottom scraper. 'I'he use the eiliciency of reforms calcium hydroxide. Willeke-f"-` especially true of the I ltion, and from 3% to 12% uable fibers and fillers. In place of settling tanks the white waters may be treated in like manner with our improved dled by any of the commercial separating devices. The use of our improved agglomerating solution is particularly desirable with apparatus of the kind which introduces finely divided air bubbles into the white water, the agglomerated fiber and suerheinsnoated by v scrapers on equipment occupying relative small space, with continuous action and providing in many cases an eiiluent carrying less than 0.5 poundof illterable solids'per 1000 gallons of efnuent.

'I'he use of the improved agglomerating solution is also applicable in the treatment of process waters. such as the removal of muds in the washing oi' sands, permitting re-use of the clarified Y water. In this case, the auxiliary composition of matter is added to the muddy process water just before passing to large settling tanks of the type generally used in the trade. The agglomerating actions takes place at once, permitting the muds to settle rapidly, the clarified overow emuent is then suitable for re-use in the continued washing of the sand. y

In addition to the above examples. our improved agglomerating solutions are applicable to many other uses for separation of solids from liquids, such as to coal mine wastes. distillery wastes', sewage, tannery wastes, raw waters, process waters, and industrialwastes where the recovery of suspended solids or clarication of turbid waters for re-use is desired, or where prevention of stream pollution is an important factor.

We claim as our, invention:

1. An agglomerating composition for use with a mordanted aqueous suspension of solids having a pH of approximately froml 4.0 to 6.0, comprismildly alkaline water-soluble soap-likev colloid,

said colloid being present to the extent of from 3% to 12% dry basis based on the weight of glue.

2. An agglomerating composition for use with a mordanted aqueous suspension of solids having a pH of approximately from 4.0 to 6.0, comprising an approximately 1% solution of animal glue in water, and from-0.5% to 3.0% caustic alkali, based on the weight of the dry glue in the solurosln size, dry basis and also based on the weight of said dry glue.

3. An agglomerating composition for use with a mordantedaqueous suspension of solids having a pH of approximately from 4.0 to 6.0, without appreciably changing the pH of said suspension comprising an approximately 1% solution oi' animal glue in water in which the negative electrical charges on the glue particles are increased by the addition of from 0.5% to 12.0% of an alkali selected from a group consisting of borax, calcium hydroxide, ammonia, trisodium phosphate, silicate of soda, soda ash, sodium hydroxide, potassium hydroxide and sodium carbonate sumcient to give a resultant pH of 8.0 to 10.0.

4. An agglomerating composition for use with a mordanted aqueous suspension of solids havagglomerating agent and han- "airand removedby top V proximately 1% to 12 alkaline material dissolved in said solution,

sufficient to promote maximum hydration of the glue colloid and to impose on said protein negative electrical charges, which, when said solution is tralize the to 12.0% (as required) hydroxide, ammonia, trisodium to 12% of rosin size. 5. A composition for eiecting agglomeration of a mordanted slightly acid suspension of solids in a liquid, to facilitate the .removal ofthe solids from the liquid, animal glue dissolved in water to form an apand from 9.5% i

said composition comprising an protein solution,

added to a suspension of solids in a liquid, neuelectrical charges of said solids and thereby cause agglomeration of the same without coagulation of said protein.

6. A composition for eecting` agglomeration of;

1% solution of animal 3 2.0 a coalescing agent for .Y 8 v a mordanted slightly acid suspension of solids having positive electrical charges; said composition including an approximately 1% animal glue solution and sufiicient alkali to produce a solution having a pH in the range of 8.0 to `10.0 and'to impose negative electricabcharges on the glue protein. which negative charges neutralize the positive charges of said solids when said solution is added to said suspension, to cause agglomeration of said solids.

7. An agglomerating composition for use withv va mordanted aqueous suspension of solids having a pH of approximately from 4.0 to 6.0, comprising a dilute solution of animal glue in water, sumcient alkali to give the solution a pH of .approximately 8.0 to 10.0 and to impose negative electrical charges on said glue, and from 3% to 12% based on the dry weight of glue of a mildly alkaline water-soluble soap-like colloid which constitutes said solids.

RICHARD TUTT,Jn. JOHN R.HUBBARD. CHARLES R. MCKEE. 

